JP3265240B2 - Novel (meth) acrylic resin compositions for marine antifouling paints and corresponding paint compositions - Google Patents

Abstract

Organo-soluble methacrylic or acrylic resin compositions including a polymer containing units derived from methacrylic acid esterified with -Ti(OR)3 groups mixed with free Ti(OR)4 which represents the excess of the Ti(OR)4 introduced in an amount sufficient for the resulting composition to be organo-soluble and not in the form of a gel. R = ethyl, isopropyl, n-butyl, t-butyl, 2-ethylhexyl or t-amyl.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
The present invention relates to a method for producing a (meth) acrylic resin for ship antifouling paint, which has a nt) and has no harmful biochemical effect on the marine environment, and a paint composition thereof.

[0002]

2. Description of the Related Art Self-cleaning paints based on organotin derivatives were developed in the 1960s and have been widely used worldwide. When this binder is used, the activation time becomes longer, the same performance can be maintained even if the amount of the active substance is reduced, and advantages such as elimination of the phenomenon of intermetallic corrosion are obtained. In contrast to conventional paints, self-cleaning paints can release a certain active species continuously over time. Also, the progressive erosion of the polymer improves the surface condition and reduces the roughening of the ship's wall before docking the ship. However, many studies have shown that the use of high concentrations of tin results in abnormal oyster calcification and reduced oyster larvae capture. As a result of these studies, the use of tin derivatives on ships less than 25 meters long has been banned in France, and other countries have similar regulations.

Since then, an important goal has been to study new resins that impart similar self-cleaning properties to antifouling paint films. As a result, polymers having triorganosilyl units with excellent self-cleaning properties have been developed by many companies, but have the disadvantage of being expensive.

[0004] In order to solve this problem, it has been considered to use titanium, which is known to be stable and non-toxic in oxide form, instead of silicon. The use of acrylic monomers having titanate groups as fillers in marine antifouling coating compositions to produce crosslinked polymer particles has been described in a number of patents: Japanese Patent No. 57565/87, European Patent No. 286243, Japanese Patent No. 57564/87, Japanese Patent No. 86-217781, European Patent No. 260958, Japanese Patent 86-
200344, European Patent No. 259096. These particles have the property of disintegrating in a weakly basic medium, especially in seawater, and are said to be self-cleaning coating films. However, these patents do not describe a method for producing an organic-soluble resin that can be used as a binder in a marine antifouling coating composition.

[0005]

The inventor of the present invention has found that, although the stoichiometric amount used in the examples of the above patents produces a gel upon esterification, it is surprising that a polymer having methacrylic acid groups is produced. It has been found that when esterifying with tetraalkoxytitanium, an excess amount of tetraalkoxytitanium relative to the acid groups results in an organically soluble reactant that can be used as a binder in marine paints. The same also occurs when radically copolymerizing tetraalkoxytitanium methacrylate with at least one comonomer in the presence of tetraalkoxytitanium.

In both cases, the resulting materials are soluble in common organic solvents (toluene, xylene, alcohol esters, etc.) and are generally produced in these solvents. However, after evaporation of the solvent, it is no longer soluble (in said solvent). The erosion rates of coatings (paints) made using these materials as binders are constant over time when directly evaluated with paint formulations.

[0007]

The first object of the present invention is to
Polymers having units derived from methacrylic acid esterified with Ti (OR) ₃ groups (R is ethyl, isopropyl,
n-butyl, t-butyl, 2-ethylhexyl and t-amyl), and the polymer is mixed with free Ti (OR) ₄ to form the free Ti (OR) ₄ is characterized by being an excess of Ti (OR) ₄ introduced in an amount sufficient to prevent the resulting composition from being organically soluble and not gelling during the production of the polymer. Organic soluble (meth) acrylic resin composition.

In general, the greater the steric hindrance of the radical R, the less excess Ti (OR) ₄ required to obtain the organic soluble composition.

Preferred examples of the organic soluble composition of the present invention include the following (the total of the esterified polymer and the free Ti (OR) ₄ is 100%):

[0010]

The esterified polymer comprises units of esterified methacrylic acid and alkyl (meth) acrylates such as methyl methacrylate and butyl methacrylate, especially C 1 -C
It can be a copolymer containing units of at least one comonomer selected from 6 alkyl (meth) acrylates.

The organic soluble composition of the present invention is generally in a solvent consisting of an alcohol ether such as toluene, xylene, 2-methoxyethanol or 1-methoxy-2-propanol or a mixture thereof, The solids content is generally about 20-80% by weight, preferably about 30-80% by weight.
60% by weight.

In a first embodiment of the present invention, the organic soluble composition is a product obtained by esterifying a polymer having units derived from methacrylic acid with Ti (OR) ₄ in a solvent,
At this time, the molar ratio of Ti / COOH is 1 or more and up to 17/1, but can exceed this, preferably 3 /
Between 1 and 10/1.

In a second embodiment of the present invention, the organic soluble composition comprises at least one methacrylic acid esterified with Ti (OR) ₃ in a solvent and in the presence of Ti (OR) ₄ , and at least one comonomer. In this case, the reaction between methacrylic acid and Ti (OR) 4 is performed at a molar ratio of 1 / x (x> 1), and the range of the Ti / COOH molar ratio is It can be the same as one embodiment.

The applicant's co-pending French patent application "Unsaturated organometallic compounds of titanium and a process for its preparation" describes compounds (I) of the formula (I):

Embedded image (Where R = tert-butyl, tert-amyl or 2-ethylhexyl)

Compound (I) is prepared by converting methacrylic acid and tetraalkoxytitanium Ti (OR) ₄ (R = isopropyl or tert-
Butyl) to give the corresponding compound (I)
It can be produced by reacting methacrylic acid with Ti (OR) (OtAm) ₃ (R = isopropyl or tert-butyl, tAm = tert-amyl) to obtain a compound (I) of R = tert-amyl. R = Isopropyl or tert-butyl compound
(I) as a synthetic intermediate, tert-amyl alcohol or
Reaction with 2-ethylhexanol gives compounds (I) wherein R is tert-amyl or 2-ethylhexyl. Methods for preparing compounds where R = ethyl, isopropyl and n-butyl are known.

The polymerization conditions used in the preparation of the resins of the present invention are well known to those skilled in the art, and the polymerization is carried out at a temperature of 40 to 85 ° C. in a proportion of 0.05 to 1.5% by weight of azobis Isobutyronitrile (AI commercially available from Elf Atchem)
An azo radical initiator such as BN or AZDN) or 2,2-azobis (2,4-dimethylvaleronitrile) or a peroxide radical initiator such as dibenzoyl peroxide; and excess Ti (OR) ₄ In the presence of In the latter case, the organic soluble composition may contain the ROH formed when methacrylic acid is esterified with Ti (OR) ₄ , and the crude product of this esterification participates in the copolymerization reaction. in this case,
The produced alcohol serves as a cosolvent.

Another object of the present invention is a marine antifouling paint composition, characterized in that it contains a composition as defined above as a binder. It is present in the binder coating composition, for example, in a proportion of 30 to 40% by weight of the whole.

The coating composition may conventionally contain the usual ingredients such as: 1) soy lecithin, modified hydrogenated castor oil, viscosity stabilizer (such as Viscostab CNF 896 from Elf Aquitaine). ) Pigments and fillers such as non-acicular zinc oxide, cuprous oxide and rutile titanium oxide 3) Solvents and diluents such as solvent naphtha, toluene and xylene

Hereinafter, non-limiting examples of the present invention will be described.

EXAMPLES The resins used are part of the following Elvacite® series, manufactured by ICI and supplied to applicant by SPCI: Elvacite 2550: methacrylic copolymer. 1H NMR and 13C NMR analysis revealed a methacrylic acid (MAA) -methyl methacrylate (MMA) -n-butyl methacrylate (BuMA) terpolymer (4-14-82 molar ratio). Acid index indicated by the manufacturer = 17; Tg =
36 ° C: Mn = 57,700, Mw = 120,700, I = 2.09 (molecular weight measured by GPC). Elvacite 2669: A slightly alkaline, water-soluble acrylic resin. It is a tetrapolymer containing units of methyl methacrylate, ethyl methacrylate and ethyl acrylate in addition to methacrylic acid. Molecular weight indicated by manufacturer = 6
0,000; Tg = 100 ° C. In the following examples, SC is dry solids, nBu is n-butyl,
EH means 2-ethylhexyl, respectively.

Example 1 Elvacite (Registered trademark) 2550 Resin with Ti (OnBu)
5 g of Elvacite® 2550 resin was dissolved in 20 g of anhydrous toluene in a 100 ml single-necked round bottom flask with Ti / COOH molar ratio = 7/1, SC = 30% . Next, 3.62 g of pure tetrabutoxytitanium were added and the mixture was stirred vigorously. A significant increase in the viscosity of the mixture was immediately observed, and the mixture immediately turned into a clear, homogeneous solution of intermediate viscosity. This solution is stable if stored in a closed container. The reaction was performed at low temperature. The esterified polymer showed excellent solubility in anhydrous toluene or anhydrous xylene.

[0022]

Example 2 Esthetic treatment of Elvacite® 2550 resin with Ti (OEH) 4
Le of Ti / COOH molar ratio at 4/1, SC = 30% 100 ml Tankuchimaru bottomed flask, was dissolved 5g of Elvacite (R) 2550 resin in anhydrous toluene 19.8 g. Next, 3.50 g of pure tetra (2-ethylhexoxy) titanium was added and the mixture was stirred vigorously. The viscosity of the mixture increases sharply and sharply, after which the viscosity slowly decreases,
Eventually, a stable and homogeneous viscous solution was obtained. The reaction was performed at low temperature. The esterified polymer showed excellent solubility in anhydrous toluene or anhydrous xylene.

[0024]

Example 3 Elvacite (Registered trademark) 2669 resin using Ti (OEH) ₄
Etherified Ti / COOH molar ratio = 3/1, SC = of 50% 100 ml Tankuchimaru bottomed flask with 1 g Elvacite The 669 resin was dissolved in 4.75 g of anhydrous 2-methoxyethanol. Next, 1.25 g of pure tetra (2-ethylhexoxy) titanium was added and the mixture was stirred vigorously. The viscosity of the mixture rapidly increased and then decreased gradually to finally obtain a stable homogeneous viscous liquid solution. The reaction was performed at low temperature. Anhydrous toluene or xylene was added to the obtained esterified polymer solution, but there was no problem with the compatibility. Toluene (or xylene) is Ti (O
EH) ₄ can also be added before adding.

[0026]

Example 4 Esthetic using (OEH) ₄ of Elvacite® 2669 resin
Le of Titi / COOH molar ratio = 5/1, SC = 50 % 100 ml Tankuchimaru bottom in a flask of 1g lvacite 2669 resin was dissolved in 3.11 g of anhydrous 2-methoxyethanol. Next, 4.14 g of anhydrous toluene was added and the mixture was stirred for several minutes. Then 6.25 g i (OEH) ₄ was added and the mixture was stirred vigorously. The viscosity of the mixture increased rapidly and then slowly changed to a liquid, resulting in a viscous, homogeneous mixture. This mixture is stable if stored in a sealed container. This reaction is performed at low temperature.

[0028]

[0029]Example 5  The procedure was as in Example 4, but with 2-methoxyethanol.
Instead, add 1-methoxy-2-propanol and
Xylene in place of the solvent, and the solvent used is anhydrous.
You.

Examples 6-8 Antifouling paint formulations The following compositions were formulated (amounts are expressed in weight percent).

[Table 1]

The order of addition is as follows. 1. Binder 2. Soy lecithin 3. Reformed hydrogenated castor oil 4. Rutile titanium oxide 5. Zinc oxide 6. Cuprous oxide 7. Solvent

The ingredients are weighed and added continuously to a porcelain jar to produce a formulation in about 10 minutes to 1/4 hour. Do not leave the jar open between weighings. Once all the ingredients have been added, porcelain balls of various diameters are placed, the jar is closed and the mixture is kneaded securely. The powder of the three formulations is about 50 μm. Milling was performed using a planetary mill (minimum 12 hours, maximum 24 hours). The amount of esterified Elvacite® copolymer in the formulations of Examples 6, 7 was 5.90% and the amount of excess Ti (OEH) ₄ was 13% (percent by weight). The dry copolymer in the formulation of Example 8
18.60% by weight, the binder of Example 6 had a weight ratio of 2-methoxyethanol / toluene of 43/57, and the binder of Example 7 had 1-methoxy-2-propanol /
The weight ratio of xylene was 43/57.

Example 9 A formulation was prepared by adding 10% by weight of dibutyl phthalate to the dry binder as a plasticizer to the formulation of Example 7.

EXAMPLE 10 The erosion test conditions using a turbo eroder (Turbo-eroder ") are as follows: a cylinder (φ = 4-5 cm) is attached to the motor by a central shaft to prevent the formation of vortices, and Place the cylinder and turbine in a 40 liter tank at a temperature of 40 ° C and a pH of 8.3. Immerse in a cell containing STM seawater. The motor runs at 620 revolutions per minute or 40 knots. A different formulation is applied to the lower half of each cylinder. One is the formulation of the comparative example. [Table 2] shows the thickness loss (μm) measured over time as a whole.

[0035]

[Table 2] It can be seen that the thickness loss (erosion rate) is a linear function of time.

Examples 11 to 14 Methyl methacrylate (MMA) / tri-n-methacrylate
Butoxytitanium (MAA-Ti nBu) Copolymer General Procedure A methacrylic acid (MMA) is reacted equimolarly with Ti (OnBu) ₄ to make “MAA-Ti nBu”, and butanol is removed by distillation. Adding "MAA-Ti nBu" a sufficient amount of Ti molar ratio 1 / x, corresponding to a reaction between methacrylic acid and _{Ti (OnBu) 4 (OnBu)} 4. In the copolymerization, the molar ratio of MMA / MAA-Ti nBu was 95/5.
Set to. This corresponds to 35.8 / 64.2 when x = 7 and 35.8 / 64.2 when x = 10. This calculation is performed by combining the excess Ti (OnBu) ₄ and “MAA-Ti nBu”. The reaction is carried out in a closed vessel, and various reactants, an anhydrous solvent (toluene) and a polymerization initiator ((AIVN)) are introduced. This polymerization initiator is 0.1% based on the total weight of MMA + MAA-Ti nBu.
% By weight (MAA-Ti nBu includes excess Ti (OnBu) ₄ ). After degassing three times by freeze-vacuum thawing, the sealed container is sealed and immersed in a bath adjusted to 60 ° C. for 24 hours. The results obtained by changing the polymerization conditions are summarized in [Table 3].

[0037]

[Table 3]

[0038]

[0039]

EXAMPLES 15-18 Methyl methacrylate (MMA) and trimethacrylate (2-
Ethylhexoxy) copolymerization with titanium (MAA-Ti EH) MAA-Ti EH "+ 2-ethylhexanol + excess Ti (OEH) ₄ mixed
General procedure for directly obtaining MAA-Ti EH by mixing MAA and Ti (OEH) ₄ in a mole ratio of 1/4
make. 1 reaction occurs equivalent of MAA and 1 equivalent of Ti (OEH) ₄ 4, resulting 2-ethylhexanol remains in the mixture. Thus, there are three equivalents of excess Ti (OEH) ₄ . The reaction is performed in a sealable test tube. Introduce each reactant, anhydrous solvent (toluene) and initiator (AIVN). The initiator is the monomer (MAA + MAA-Ti EH total weight, excess Ti (OE
H) 4) at a ratio of 0.1% by weight. After degassing the mixture, the tube is sealed and immersed in a bath thermostated at 60 ° C. for 48 hours. The results obtained by changing the polymerization conditions are summarized in [Table 4].

[0041]

[Table 4] * Excess Ti (OEH) ₄ was included in MAA-Ti EH and calculated.

[0042]

[0043]

[0044]Example 19 (comparative example) and 20-21 (this invention
Akira) Methyl methacrylate (MMA) and trimethacrylate (2-
Copolymerization with (ethylhexoxy) titanium (MAA-Ti EH) Example 2 of patent application showing MAA-Ti EH in Examples 11-14
Produced as described in Next, MAA-Ti EH
3 equivalents of Ti (OEH)_Four(Examples 20-21). Example
At 19, this mixing is not performed. Copolymerization is described in Examples 11-18.
Perform for 48 hours at 60 ° C. in toluene as described above. This and
MMA + MAA-TiEH (excess Ti (OEH)_FourTo the total amount of
On the other hand, 0.1% by weight of AIVN is used as initiator.

Table 5 shows the results obtained by changing the polymerization conditions.
Are shown together.

[Table 5] * Defined in Examples 11-14 ** Calculated including excess Ti (OEH) ₄

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Jean-Louis Vernet France 83210 La Farrede Residence Lamborgh 25 (72) Inventor Marie Amber France 13001 Marseille Rue Disoial 41a (58) Fields studied (Int.Cl. ⁷ , DB name) C08L 33/14 C08K 3/22 C08K 5/00 C08K 5/56 C09D 133/14 CA, REGISTRY (STN)

Claims (14)

(57) [Claims] 1. A unit derived from methacrylic acid esterified with a -T i (OR) ₃ group and an alkyl (meth) acrylate
A copolymer comprising a comonomer unit of
Over a mixed free Ti (OR) ₄ and organic soluble including
A (meth) acrylic resin composition , wherein the free
Ti (OR) ₄ is an excess amount of Ti (OR) ₄ introduced in the production of the polymer in an amount sufficient to make the resulting composition organically soluble and not gelled, wherein the R is D
Tyl, isopropyl, n-butyl, t-butyl, 2-ethylhexyl
Any one selected from sill and t-amyl
(Meth) acrylic resin composition of the organic soluble, characterized in that representing the. 2. Esterified polymer + free Ti (OR) ₄
The composition according to claim 1, wherein the composition has the following ratio when the whole of the composition is 100% by weight : 3. An alkyl (meth) acrylate of a comonomer unit.
Relate is C1-C6 alkyl (meth) acrylate
The resin composition according to claim 1 or 2 . Wherein toluene, xylene, alcohol Ruete
Le or claim comprising a solvent consisting of mixtures 1 or
The resin composition according to the other two. 5. The method according to claim 5, wherein the alcohol ether is 2-methoxyethanol.
Or 1-methoxy-2-propanol or a mixture thereof
The resin composition according to claim 3, comprising a compound . 6. The method according to claim 1, wherein the solid content is 20 to 80% by weight.
The composition according to any one of 5. 7. A copolymer obtained by esterification,
Any one of claims 1 to 6 copolymer containing units derived the Ti / COOH molar ratio of methacrylic acid in a solvent in the one or more products which are obtained by esterifying at Ti (OR) ₄ A composition according to claim 1. 8. The Ti / COOH molar ratio is from 3/1 to 10/1.
Set composition as claimed in claim 7. 9. Ti in a solvent (OR) ₃ in the esterified least one kind of methacrylic acid and at least one kind of comonomer, in the presence of Ti (OR) _4, methacrylic acid and Ti (OR) _Four
Reaction such that the molar ratio 1 / x (x> 1) , A composition according to any one of radical copolymerization with claim 1 that obtained 8 with. 10. The crude esterification product is subjected to a copolymerization reaction.
Using the composition of claim 9 including the resulting et <br/> Re that ROH is esterified methacrylic acid with Ti (OR) _4. 11. according to any one of claims 1-10
A marine antifouling paint composition comprising the composition of claim 1 as a binder. 12. The coating composition according to claim 11 binder amount in the coating composition is 30 to 40% by weight of the total composition <br/>. 13. An auxiliary, a pigment, a filler, a solvent and a diluent.
At least one selected from the group consisting of
The coating composition according to claim 11 or 12, further comprising: 14. An adjuvant comprising soy lecithin, modified hydrogenated kiln.
Pigments or viscosity stabilizers, pigments and
And filler is non-acicular zinc oxide, cuprous oxide or rutile
Solvent and diluent selected from titanium oxide
Contracts selected from ntnaphtha, toluene or xylene
14. The composition according to any one of claims 11 to 13 .